Ultrasonic Measurement of Sub-Micron Particles

Based on technology described in a Du Pont patent for an offline system, we have developed a prototype in-line ultrasonic cell for measuring particle size distribution. We have used this cell to verify the Allegra-Hawley model of ultrasonic attenuation in dilute (< 5 % vol) slurries of sub-micron ceramic particles, and we are developing a model that can cope with the multiple scattering effects occuring at higher concentrations. In this paper we present the results of attenuation measurements for ultrasound (2–50 MHz) in slurries with concentrations ranging from 0.5 010 to 38 010 (vol). The attenuation is proportional to slurry concentration up to 5 010 (vol) and is predicted by single scattering models. Above approximately 100% concentration, the attenuation is actually lower than expected. For the dilute slurries we find excellent agreement between our measurements and the Allegra-Hawley calculations, and the effects of the particle size distribution are evident in the ultrasonic attenuation spectrum. These ultrasonic data can be inverted to determine the particle size and concentration in aqueous slurries of sub-micron particles.     

Measuring fluid and slurry density and solids concentration non-invasively

Staff at Pacific Northwest National Laboratory have developed a highly sensitive, non-invasive, self-calibrating, on-line sensor to measure the density, speed of sound, and attenuation of ultrasound for a liquid or slurry flowing through a pipeline; the approach can also be applied for measurements made in vessels. The sensor transducers are mounted directly upon the stainless steel wall and the pipeline wall becomes part of the measurement system. Multiple reflections within the stainless steel wall are used to determine the acoustic impedance of the liquid, where the acoustic impedance is defined as the product of the density and the speed of sound. The probe becomes self-calibrating because variations in the pulser voltage do not affect the measurements. This feature leads to the stability of the measurements and the instrument requires much less time and effort to calibrate. Further, the calibration remains constant in time, because it does not depend upon the pulser voltage remaining at a given value. By basing the measurement upon multiple reflections, the sensitivity of the measurement is significantly increased. For slurries with wt% solids concentration of 1% or less, high sensitivity is gained by analyzing attenuation measurements obtained from multiple paths through the slurry. For slurries with higher concentrations of solids, sufficient sensitivity is obtained by analyzing data from a simple transmission. Data are presented that show probe performance for each of these cases: very dilute and highly concentrated kaolin clay slurries.     

On-Line Particle Size Analysis Using Ultrasonic Velocity Spectrometry

A new method is described for the determination of particle size distribution of slurries based on ultrasonic velocity spectrometry combined with gamma-ray transmission. This method shares the advantages of ultrasonic attenuation spectroscopy of being capable of analyzing highly concentrated samples without dilution. However the ultrasonic velocity method is better suited to fine particles of diameter from about 0.1 to 30 μm, a greater volume of slurry is analysed and therefore sampling errors are reduced, and precise theoretical models are readily available to permit the accurate determination of size distribution by inversion of ultrasonic velocity measurements. The method can also be used to accurately determine particle size cut points by linear correlation. Using either inversion or correlation methods, the accuracy of particle size information from ultrasonic velocity spectroscopy is significantly enhanced by the independent measurement of solids loading by gamma-ray transmission. In addition, larger sizes can be measured by combining the ultrasonic velocity method with ultrasonic attenuation measurements. The method has been tested in the laboratory on a wide variety of mineral and paint slurries. The method determined the size distribution of single component silica and alumina samples in water in agreement with laser diffraction measurements and the method successfully distinguished well and poorly dispersed TiO₂ suspensions. For composite samples the method discriminated separate TiO₂ and CaCO₃, components and determined their proportions to within 0.25% volume. In addition the method, in combination with ultrasonic attenuation measurements, determined the size fractions of iron ore slurries below 10 and 30 μm to within 1.3% and 1.0% relative respectively, when compared with laser diffraction measurement of particle size. The CSIRO is presently designing an industrial gauge which will be manufactured and installed in an industrial slurry stream in 1997.     

Particle Size Distribution Analysis of Industrial Colloidal Slurries using ultrasonic spectroscopy

Several solid-liquid suspensions containing submicron particles at moderate to high concentrations (5 to 50 volume percent) are encountered in industrial slurry processing. Measurements of ultrasonic attenuation spectra are used in a newly developed AcoustoPhor particle analysis system to get particle size distributions of such colloidal suspensions. This paper deals with the performance evaluation of the AcoustoPhor system. The automated ultrasonic spectrometer component of the AcoustoPhor system was tested using a reference silicone liquid for its accuracy and precision. The particle size distribution (PSD) estimation capabilities were evaluated using a set of well-dispersed slurries covering a wide range of particle concentrations. Sensitivity to process variations was evaluated in field tests at a pigment manufacturing plant. The AcoustoPhor system appears to be capable of providing reliable PSD data for inorganic pigment slurries with particle diameters ranging from 0.01 to 100 micrometers at particle concentrations as high as 50 volume percent.     

四丁基溴化铵水合物浆体导热系数测量研究

四丁基溴化铵(TBAB)水合物浆体在常压下的相变温度介于0-12℃之间,作为蓄冷材料使用时由于相变过程的存在使得其蓄冷能力较高,而且在管道中具有良好的流动特性,因而是一种理想的蓄冷和冷量输送材料。对比分析了传统导热系数计算公式和基于一维非稳态导热模型导出的导热系数计算公式的区别。利用热线装置分别测量了TBAB溶液和水合物浆体的导热系数。实验得出5-30 wt%TBAB溶液的导热系数在0.4-0.6 W.m-1.K-1之间,并随浓度的增加而减小;10-40vol%的水合物浆体的导热系数在0.5-0.6 W.m-1.K-1之间,并随体积分数的增加而增大;相同体积浓度时A型水合物浆体的导热系数大于B型水合物浆体的导热系数。     

Rheological behaviour of ethylene glycol-titanate nanotube nanofluids

Experimental work has been performed on the rheological behaviour of ethylene glycol based nanofluids containing titanate nanotubes over 20–60 °C and a particle mass concentration of 0–8%. It is found that the nanofluids show shear-thinning behaviour particularly at particle concentrations in excess of ~2%. Temperature imposes a very strong effect on the rheological behaviour of the nanofluids with higher temperatures giving stronger shear thinning. For a given particle concentration, there exists a certain shear rate below which the viscosity increases with increasing temperature, whereas the reverse occurs above such a shear rate. The normalised high-shear viscosity with respect to the base liquid viscosity, however, is independent of temperature. Further analyses suggest that the temperature effects are due to the shear-dependence of the relative contributions to the viscosity of the Brownian diffusion and convection. The analyses also suggest that a combination of particle aggregation and particle shape effects is the mechanism for the observed high-shear rheological behaviour, which is also supported by the thermal conductivity measurements and analyses.     

动态冰浆流动的浓度分布及粘性研究

动态冰浆是一种固-液两相流体。文中采用理论模型研究了动态冰浆在非均质流动情况下的冰晶浓度分布,分析了冰晶浓度、冰浆流速、管道直径、冰晶粒径大小对冰浆的动态粘度的影响。分析表明:在高冰晶浓度、低流速情况下,冰浆的平均粘度不仅和冰晶浓度和载流溶液的粘度相关,还受到冰浆流速、管道直径和冰晶颗粒大小的影响。     

Laponite: aging and shear rejuvenation of a colloidal glass

We study the nonlinear rheological behavior and the microscopic particle dynamics for a colloidal glass, to see whether recently developed models for driven glassy systems can be applied to predict the rheology. Qualitatively, all the findings predicted by the models can be retrieved in our system. Notably, the viscosity decreases strongly with the shear rate. Since it is difficult to predict non-Newtonian viscosities of colloidal systems due to long-ranged hydrodynamic interactions, this shows the promise of this approach for predicting flow behavior. In addition, the measurements allow us to relate the microscopic diffusion dynamics to the macroscopic viscosity of the system.     

Numerical Simulation of Swirl Flow Characteristics of CO2 Hydrate Slurry by Short Twisted Band

The development of oil and gas resources is gradually transferring to the deep sea, and the hydrate plugging of submarine pipelines at high pressures and low temperatures is becoming an important problem to ensure the safety of pipeline operations. The swirl flow is a new method to expand the boundary of hydrate safe flow. Numerical simulation of the hydrate slurry flow characteristics in a horizontal pipeline by twisted band has been carried out, and the flow of CO₂ hydrate slurry in low concentration has been simulated by the RSM and DPM models. The results show that the heat transfer efficiency is also related to Re and particle concentration. The velocity distribution has the form of symmetrical double peaks, and the peaks finally merge at the center of the pipeline. Vortexes firstly appear on both sides of the edge of the twisted band, and then move to the middle part of the twisted band. Finally, the vortex center almost coincides with the velocity center. The rotation direction of hydrate particles is the same as the twisted direction of the twisted band, twist rate (Y) is smaller, Re is larger, and the symmetric vortex lines merge farther away. The initial swirl number is mainly related to Y, but not Re. The swirl flow attenuates exponentially, and its attenuation rate is mainly related to Re, but not Y. Compared with ordinary pipelines, the swirl flow can obviously improve the transportation distance of hydrate slurry.     

Ultrasonic wave propagation in concentrated slurries – The modelling problem

The suspended particle size distribution in slurries can, in principle, be estimated from measured ultrasonic wave attenuation across a frequency band in the 10s of MHz range. The procedure requires a computational model of wave propagation which incorporates scattering phenomena. These models fail at high particle concentrations due to hydrodynamic effects which they do not incorporate. This work seeks an effective viscosity and density for the medium surrounding the particles, which would enable the scattering model predictions to match experimental data for high solids loading. It is found that the required viscosity model has unphysical characteristics leading to the conclusion that a simple effective medium modification to the ECAH/LB is not possible. The paper confirms the successful results which can be obtained using core–shell scattering models, for smaller particles than had previously been studied, and outlines modifications to these which would permit rapid computation of sufficient stability to support fast particle sizing procedures.     

动态冰浆传热特性的研究

动态冰浆由于具有较强的蓄能和传热能力,日益受到人们的重视。文中建立了动态冰浆传热特性的数理模型,并利用已知的载流溶液和冰晶的物性参数,得到了动态冰浆在水平直管、等热流加热条件下的传热系数,根据计算结果,分析了传热系数随着冰浆浓度的变化的规律和冰浆流速和管径对动态冰浆传热性能的影响。     

Improvement in properties of coal water slurry by combined use of new additive and ultrasonic irradiation

Coal water slurry (CWS) was prepared with a newly developed additive from naphthalene oil. The effects of ultrasonic irradiation on coal particle size distribution (PSD), adsorption behavior of additive in coal particles and the characteristics of CWS were investigated. Results showed that ultrasonic irradiation led to a higher proportion of fine coal in CWS and increased the saturated adsorption amount of additive in coal particles. In addition, the rheological behavior and static stability of CWS irradiated by ultrasonic wave were remarkably improved. The changes on viscosity of CWS containing 1% and 2% additive are qualitatively different with the increasing sonication time studied. The reason for the different effect of sonication time on CWS viscosity is presented in this study.     

Formation of Calcium Carbonate Sub‐Micron Particles in a High Shear Stress Three‐Phase Reactor

The production of precipitated calcium carbonate (PCC) was investigated experimentally under industrially relevant conditions, i.e. at high solid concentrations and increasing amount of solid product in the slurry. Temperature is an important parameter since it determines the crystal structure, the particle shape and, as a consequence, the viscosity of the slurry. Of course, the mass concentration of the raw material also has an important influence on the viscosity. From the particle size distributions of primary particles and agglomerates, it can be concluded that the nucleation process is governed by primary nucleation. Also, heterogeneous nucleation occurs on solid calcium hydroxide particles that are present in the slurry. Especially if the raw material contains impurities heterogeneous nucleation occurs and large and unwanted particles are formed. If the slurry is not stabilized, strong agglomeration occurs that can be influenced by the shear stress introduced to the slurry: a high shear stress which is linked to the viscosity of the slurry limits the upper particle diameter and leads to a steep particle size distribution of the product.     

Measurement of viscosity and shear wave velocity of a liquid or slurry for on-line process control

An on-line sensor to measure the density of a liquid or slurry, based on longitudinal wave reflection at the solid-fluid interface, has been developed by the staff at Pacific Northwest National Laboratory. The objective of this research is to employ shear wave reflection at the solid-fluid interface to provide an on-line measurement of viscosity as well. Both measurements are of great interest for process control in many industries. Shear wave reflection measurements were conducted for a variety of liquids. By analyzing multiple reflections within the solid (only 0.63 cm thick-similar to pipe wall thickness) we increased the sensitivity of the measurement. At the sixth echo, sensitivity was increased sufficiently and this echo was used for fluid interrogation. Shear wave propagation of ultrasound in liquids is dependent upon the viscosity and the shear modulus. The data are analyzed using the theory for light liquids (such as water and sugar water solutions) and also using the theory for highly viscous liquids (such as silicone oils). The results show that, for light liquids, the shear wave reflection measurements interrogate the viscosity. However, for highly viscous liquids, it is the shear wave modulus that dominates the shear wave reflection. Since the density is known, the shear wave velocity in the liquid can be determined from the shear wave modulus. The results show that shear wave velocities in silicone oils are very small and range from 315 to 2389 cm/s. Shear wave reflection measurements are perhaps the only way that shear wave velocity in liquids can be determined, because the shear waves in liquids are highly attenuated. These results show that, depending on the fluid characteristics, either the viscosity or the shear wave velocity can be used for process control. There are several novel features of this sensor: (1) The sensor can be mounted as part of the wall of a pipeline or tank or submerged in a tank. (2) The sensor is very compact and can be located within the process stream. (3) The sensor can interrogate and characterize very attenuative liquids or slurries because the sensor operation depends upon reflection at the interface between the solid and the fluid, rather than on transmission through a liquid. (4) The sensor performance is not affected by fluid flow rate, entrained air, or vibration.     

Modelling of decomposition of a single gas hydrate particle in water behind the shock wave front

The mathematical model of decomposition of a spherical gas hydrate particle in water behind a 1D wave of the stepped profile (rarefaction wave) is suggested. Contribution of the outer and inner heat flux in a particle to the process of hydrate decomposition is studied. The effect of the gas hydrate particle size, pressure and temperature jumps in liquid on gas hydrate decomposition is investigated.     

四丁基溴化铵水合物浆在蓄冷空调中的应用前景

TBAB水合物浆作为适用于空调工况的新型两相潜热输送载冷剂,可以大幅度降低冷量输送的功耗。通过添加成核剂的方法来降低所需的过冷度,制备方法简单节能,而且蓄冷特性出色,相变蓄冷温度与溶液的浓度密切相关,可通过调节溶液的浓度,获得与空调冷冻水一致的相变温度。根据非牛顿流体的特点,综述了国内外关于TBAB水合物浆流变方程的选择,列出了表观粘度及传热系数的计算方法,并指出TBAB水合物浆应用于蓄冷空调中的优点。     

Origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid

We report on the investigation of the origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid.The oxide to nitride removal selectivity of the ceria slurry with picolinic acid is as high as 76.6 in the chemical mechanical polishing.By using zeta potential analyzer,particle size analyzer,horizon profilometer,thermogravimetric analysis and Fourier transform infrared spectroscopy,the pre-and the post-polished wafer surfaces as well as the pre-and the post-used ceria-based slurries are compared.Possible mechanism of high oxide to nitride selectivity with using ceria-based slurry with picolinic acid is discussed.     

Ultrasonic diffraction grating spectroscopy and the measurement of particle size

The results of measurements using ultrasonic diffraction grating spectroscopy (UDGS) are found to be dependent upon the particle size of the slurry. This illustrates the emergence of a new technique for measuring particle size. Theoretical calculations are underway to describe and predict them as well. The ultrasonic grating surface is in contact with the slurry. The diffraction grating was formed by machining triangular grooves with a periodicity of 483 microm on the flat surface of an aluminum unit with send and receive transducers fastened to it. For this experimental configuration, the ultrasonic beam strikes the back of the grating at an incident angle of 30 degrees and produces a transmitted beam of spectral order m=1 in the slurry. The angle of this transmitted beam changes with frequency and, at the critical frequency of 3.47 MHz, it is located at an angle of 90 degrees. The receive transducer measures the reflected m=0 beam at an angle of 30 degrees. At a frequency slightly less than the critical frequency, the m=1 transmitted beam no longer exists and its energy is shared with all other beams. Therefore, due to energy conservation, the signal in the receive transducer exhibits a peak at the critical frequency. During the transition, the wave interacts with the particles of the slurry and ultrasound amplitude is reduced. Therefore, the peak observed by the receive transducer is reduced, compared to that for water. Data have been obtained for slurries of polystyrene spheres, ranging in size from 215 microm to 463 microm, and for weight percentages of 1-12%. Polystyrene spheres of different diameter show differing amounts of energy loss and thus, particle size identification is possible.     

Calculation of Particle Size Distributions from Ultrasonic Measurements: A Mineral Slurry Case Study

Ultrasonic transmission measurements have been used extensively to determine the particle size of solids in slurries. This case study examines the application of mathematical inversion techniques to the determination of the particle size distribution of a mineral slurry from data collected at a minerals processing plant. A new mathematical inversion technique, based on an extension of modified Chahine iteration combined with the principle of maximum entropy has been developed. Four algorithms were constructed and used to calculate particle size distributions from synthetic and raw plant data. These incorporated modified Chahine iteration and its extension, together with two different approaches to applying a density measurement constraint on the particle size distribution. In general the algorithms performed well with regression errors below 3 %. The correlation coefficients and slopes for this technique were 0.86 and 1.35 for the weight fraction of particles less than 75 microns when compared with the laser diffraction analysis. A better match was obtained for the plant data by using the new inversion technique, into which the principle of maximum entropy has been incorporated whereas this was not the case with the synthetic data, illustrating the need to match the inversion technique to the problem.     

In-Line Particle Characterization

The characterization of industrial slurries and emulsions has traditionally relied upon off-line measurements of particle size and shape. Recent advances in sensor technology have made it possible to implement in-line particle characterization on a number of industrial processes, including comminution, crystallization, and emulsification. This paper presents several recent applications of two in-line instruments developed in our laboratory: an ultrasonic instrument used to monitor particle size in slurries during milling operations and to determine droplet sizes in emulsions, and a new in-line video camera for observing the morphology of crystals produced in a commercial process.